Alkane sulfonic acid esters substituted in beta-position by ether groups and their production



United States Patent "ice .9 claims... (014 60-14 This invention relatesto the production of substituted alkaue sulfonic acid esters whichcontain an ether group in B-position to the sulfonic ester group.

It is known to prepare 3-ethoxypropylsulfonic acid ethyl ester frompropene-(2)-sulfonyl chloride and etha- 1101 in the presence of anexcess of potassium hydroxide. It is further known thatS-ethoxy-ethanesulfonic acid ethyl ester can be obtained from3-chloroethanesulfonic acid chloride and sodium ethylatel According tothese known methods, there are obtained merely alkoxyalkanesulfouic acidalkyl esters in which the alkyl groups of the ester group, and the.ether group. are identical.

The known B-alkoxyalkanesulfonic acid esters have no plasticizerproperties for polyvinyl chloride. Neither do mixtures of alkanesulfonicacid esters obtained by sulfochlorination of alkanes and esterification,which are also known, owing to the indefinite chain length or the alkylradical,

It is an object of this invention to provide new alkanesulfonic acidesters containing an. ether group in p-position. It is another object ofthe invention to provide a process for the production of alkanesulfonicacid esters substituted in li -position by an ether group whose organicradical s, different from the organic'radical in the ester group, It: isanother object of this invention to prepare alkanesulfonic acid estersetherified in B-position in which the: etheri-ied alkane radical: has a'definite chain length. It. is further an object of this invention toprovide a p oce s ar h production of. new plasticizersforpolyvinylchloride.

These objects are. achieved by reaeting a vinylsulfonic aci e e f an phac or ys oa i rhatis alcoh l, phe- 1 gr ncle r-s bstituted pheno h said et r ein t ts sdsr unsub ti uted n, ne or b t-h carbon at ms of the vinylgroup by alkyl groups, in the presence of a small amount of an alkali oralkaline earth metal; alcoholate, dry powdered alkali hydroxide orquaternary ammonium base of the formula:

in which R, R and R' denote alkyl groups with 1 to 3 carbon atoms andR"" denotes an aryl radicalrwith 610,.

10 carbon ato s w s 2 s shes tom in the r n reacted with an excessamount of an alcohol,

The sultonie acid esters which may be used as initial materials arederived from vinylsulfonic acid or from vinylsulfonic acids substitutedin 04- and/or sf-position to the sulfonic acid group by alkyl groups,especially me l t y w vl o p as id m ne s a d,

from alkanols or phenols or naphthols, or phenols or.

3,196,906 Patented June 22 1-965 naphthols substituted by inert groups,such as halogen atoms, alkoxy groups or thiocyanate groups, as hydroxycompounds. These esters are, readily obtained, for examp e om fl chlsethme lt lor and a responding hydroxy compound by the action oi twoequi a en s o an a a v lcsh at It is p fe a o use es e hic a e d ived ron l l z n s aci s-ms hyl nyl u fsn q i nd p onsns ul o c ac d an fr m.phe ols r nh h w c y c nta n one o t ree i rt atom r o p such as yswaps. i h 1 to 4 carbon qm i l s y r ps w t on to h e ca bo om l e a os, i.e., fluorine, chlorine, bromine or iodine, or thiocyanate groups.

For example the following may be used:

Vinylsulfonic acid methyl ester, oc-Methylvinylsulfonic acid methylester, u-Ethylvinylsulfonic acid methylester, 1 -propene-l-sulfonic acidmethyl ester, Z-methyl-l-propene-l-sulfonic acid methyl ester,Vinylsulfonic acid butyl ester, Vinylsulfonic aci-d phenyl ester, nyl uln s acid a-n phthy es v y alf ci B- ap t y ester, Vinylsulfonicacid-[5,6,7,8-tetrahydronaphthyl-( l 1 est r, v n l u o aci ere yl ter,Vinylsulfonic acid p-cresyl ester, v ny su fqni a id (ntertabuty phe yester, vinylsulfonic acid (2,6-di-tert.-butyl-4-methylphenyl) ester,inylsulfou s ac p-dodecylp nyl ste Vinylsulfonic acid p metho yPheny1ester, ia su oaic acid p-s xyphenyl ester, v ny sul nic ac d putcxyphnyl ester, ifllf fQI1i Qid o-chlorophsnyl ester, Vinylsulfonic acido-bromophenyl ester, viay ulfonic ac d priodenhe yl ester, Vinylsulfonicacid p-fluorophenyl ester, and, Vinylsulfonic acid p-thioeyanophenylester.

The reaction succeeds with a great variety of alcohols. For examplesaturated and unsaturated, linear and branched primary, secondary andtertiary monoalcohols, es e ia l those w h up to. 20 c n ato s, y eused, u h as m th no e ha ol, pr pa opr panol, allyl alcohol,l-butanoLisobutanol, 2 -butanol, tertiary butanol, 1 N ctanol, 2 Noctanol, Z-ethylhexyl alcohol,'decanols, in ar and branc e decy and tide y l ol m tures of alcohols with 16 to 18 carbon atoms such as areobtained by hydrogenation of vegetable or animal fats or at a ids tssr ac ho p lm t alcohol o l y l ohol,

Polyhydric alcohols, for example diols or triols, may also be used,especially those with 2 to 12 car-hon atoms, s sh, a hy en l c aae-A-dio u aasa -diol, butane-2,3-diol, Z-buteneAA-diol, hexane-.1,6-,diol,octane-1 1 ,8-dio1, or dodeeane-IJZ-diol. Que of the two, or more OHroup ay be e srifi d w th an a y group o hydroxyalkyl group with 1 to 4carbon atoms, for ex-, ample glycol monomethyl ether, glycol monoethylether,

diglyc ol, methyldiglycol, diglyeol butyl ether, or tri arsaaoe in allnot more than 20 carbon atoms, for example N,N-diethylaminoethanol,N,N-dimethylaminoethanol or methyl-stearyl-aminoethanol. Cycloaliphaticalcohols with to 12 carbon atoms in the ring, for example cyclopentanol,cyclohexanol, methylcyclohexanol, cycloioctanol, cyclododecanol, mayalso be used. Further, araliphatic alcohols, especially with 1 to 4carbon atoms in the hydroxyalkyl groups, are also suitable, for examplebenzyl alcohol, B-phenylethyl alcohol or phenylmethyl carbinol.

The reaction may be illustrated by the following reaction scheme:

R; denotes alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 3to 20 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms in thering, hydroxyalkyl groups with 2 to 12 carbon atoms, alkoxyalkyl groupswith 3 to 12 carbon atoms, dialkylaminoalkyl groups with 4 to 23 carbonatoms in all,

R denotes hydrogen or an alkyl group with 1 to 3 carbon atoms,

R denotes hydrogen or an alkyl group with 1 to 3 carbon atoms,

R; denotes hydrogen or an alkyl group with 1 to 3 carbon atoms,

R denotes alkyl groups with l to 6 carbon atoms, aryl groups with 6 tocarbon atoms, alkoxyaryl groups n with 7 to 13 carbon atoms, halogenarylgroups with 6 to 12 carbon atoms or thiocyanoaryl groups with 7 carbonatoms.

The reaction between the alcohols and the esters of the vinyl sulfonicacids that may be substituted in aand/or B-position by alkyl groups onlyproceeds when alkali or alkaline earth metal alcoholates or finelypowdered alkali hydroxide is present in the reaction mixture. Thealcoholate of that alcohol may be used which it is desired to add on;then it is sufiicient first to dissolve an alkali or alkaline earthmetal in the alcohol concerned. It is however, just as convenient to useother alcoholates, for example those of lower alcohols, for examplesodium methylate, sodium ethylate, sodium isopropylate, potassiumethylate, or potassium tertiary butylate. It is also sulficient to usedry, finely powdered lithium hydroxide, sodium hydroxide or potassiumhydroxide.

It is also possible to use quaternary ammonium bases of the formula:

RI RI!!! 9 Ne OH R11 R!!! in which R, R" and R' denote alkyl groups with1 to 3 carbon atoms and R"" denotes aryl radicals with 6 to 10 carbonatoms, aralkyl radicals with 7 to 9 carbon atoms or cycloalkyl radicalswith 5 to 12 carbon atoms in the ring, for example trimethylphenylammonium hydroxide, trimethyl-benzyl ammonium hydroxide, ortrimethyl-cyclohexyl ammonium hydroxide.

The amount of alkaline compound should not be less than 0.02 equivalentper mole of ester and not more than 0.1 equivalent.

The alcohol is used in an excess, for example 1.3 times thestoichiometrical amount. As a rule, a considerable excess is used, forexample 2 to 8 times the stoichiometrical amount; it is also possible touse an even higher excess, but this is seldom necessary. The alcoholthen acts simultaneously as a diluent. Moreover in the case ofpolyhydric alcohols it is in this Way made possible for only one OHgroup to react with the vinylsulfonic acid ester which may besubstituted by alkyl groups at one or both carbon atoms. The use ofinert diluents, for example saturated aliphatic or cycloaliphatic oraromatic hydrocarbons, such as octane, cyclohexane, benzene or toluene,or open or cyclic others, such as di-n-butyl ether, tetrahydrofurane,dioxane or anisol is possible, but is only an advantage when using solidinitial materials.

The reaction temperature lies between about -l0 and +100 C. It isadvantageous to mix the reactants at a lower temperature and then toheat them slowly.

The process may be carried out for example by dissolving thevinylsulfonic acid ester, that may be substituted by alkyl groups, inthe alcohol to be added on and slowly adding small amounts of alkalimetal alcoholate or finely powdered alkali hydroxide or the quaternaryammonium base and stirring constantly. The alkali or alkaline earthmetal may also be dissolved in the alcohol to be reacted and theunsaturated sulfonic acid ester slowly added while mixing well. In somecases it is expedient to continue stirring for a further period, forexample 2 to 24 hours, and/ or heating to to C. after all the reactantshave been added.

Working up can be carried out in various ways. For example small amountsof salts of the sulfonic acids etherified in B-position which have beenformed by hydrolysis may be washed out by adding water and the organiclayer subjected to fractional distillation after drying. The salts andcatalyst residues may also be precipitated by adding acetone or anotherketone, filtered olf and then fractionated, if desired after washing theketone with water and drying. The reaction mixture may also be distilleddirectly, the salts, byproducts and catalyst residues then remaining inthe distillation residue.

Alkanesulfonic acid esters substituted in fl-position by ether groupsand having the formula R OCR R HR SO R in which R to R are as abovedefined, and which contain in all at least nine carbon atoms are newcompounds. Those esters which contain an aryl or substituted arylradical in the ester group and four to twenty carbon atoms in the ethergroup are excellent plasticizers for polyvinyl chloride and may be usedlike phthalic esters. Suitable substances include the cresyl ester ofthe alkoxyethane sulfonic acid containing 10 to 18 carbon atoms in thealkoxy radical, such as decyloxyethane sulfonic acid cresylester,branched decyloxyethane sulfonic acid cresylester, and branchedtridecyloxyethane sulfonic acid cresylester.

The alkanesulfonic acid esters etherified in B-position may as a rule bedistilled under reduced pressure. The esters obtained may be saponifiedto the corresponding free acids in the usual way, for example by meansof caustic soda solution, advantageously by alcoholic caustic sodasolution. These free acids of the formula R O- CR R -CHR SO H and/or thealkali salts of these acids have surface-active properties when R in theformula contains at least six carbon atoms.

The invention is illustrated by, but not limited to, the followingexamples in which parts are by weight unless otherwise specified; theratio between parts by weight and parts by volume is the same as thatbetween the gram and the millimeter.

Example 1 184 parts of vinylsulfonic acid phenyl ester is dissolved in500 parts by volume of methanol. A total of 15 parts by volume of 28.5%(by weight) sodium methylate solution in methanol is added in the courseof several hours in small portions while stirring at room temperature.The mixture is shaken with 500 parts by volume of water and the organiclayer separated. The aqueous phase-is extracted with 50 parts by volumeof ether. The organic phase is united with the ethereal solution anddried overnight with anhydrous sodium sulfate. The ethereal solution isfiltered off from the sodium sulfate and the ether evaporated. Theresidue is distilled at 0.2 to 0.3 mm. Hg through a short column packedwith Raschig rings. parts of a fraction passing over between 90 and 145C.; is obtained which according to molecular weight determination,elementary analysis and iodine number (dodecyl-mercaptan method)consists of vinylsulfonic acid phenyl ester and B-methoxyethanesulfonicacid phenyl ester. 'The content of methoxy compound is; 135.2 parts62.5% of th'etheory).

r d of residue, 111 parts of [i-(n-octyloxy)-ethanesulfonic acid phenylester may be isolated (71% of the theory), boiling point 163 to 175 C.at 1.2 to.0.0.5 mm. Hg.

y P e i g in. the w y des ri ed in this examp but using 500 parts byvolume of other alcohols, the following results are obtained:

Percent Example 1 Alcohol End product Boiling point Yield of the theory6; u-Decyl alcohol. fl-(n-decyloxy)-ethanesul- 170-180 0., 0.2 mm. 14082 1 ionic acid phenyl ester. Hg. 7- Branched dcoylB-(decyloxy)-cthanesulfonic 160172 0., 0.1-0.05 mm. 134 78. 5

alco acid phenyl ester. Hg. 8;- Branched tridecylfl-(tridecyloxy)-ethanesull82191 0., 0.10.05 mm. 161 84 alcohol. ionicacid phenyl ester. Hg. 9; Benzyl alcohl fi-(benzyloxy)-ethanesul-168-182 0., 0.1-0.2 mm. 103 71 fonic acid phenyl ester. Hg.

Example. 2 Example 10 Pa ts o odium et a d so d n 0. pa by volumeof'isopropanol and, while stirrin 92 parts of vinylsulfonicacid phenylester is added at such a rate that the temperature does not rise above40 C. The mixture is then stirred for 2% hours at 30 to 40 C and, foranother 18 hours at room temperature and shaken up twice with 300 partsby volume of water. The aqueous phase is, then extracted with 50 partsby volume of ether and the ethereal solution and the organic layer aretogetherdriedwith anhydrous sodium sulfate. By fractionation, 92- partsof {3-.(isopropyloxy)aethanesulfonic acid phenyl ester (715.5%. otthetheory)v of the boiling point 123 to 127 C. at 0.2 to 0.15 mm. Hgis'obtained from the ethereal solution.

xa pl 3 l-. Pa s of sodium. me a is issolved in 400 pa t volume ofn-butanol and then 92 parts of Vinylsulfonic acid phenyl ester is addedso slowly that the temperature does not rise above 60 C. The mixture isstirred for 21/2 hours at 55 to 60 C. after the addition of another 0Par s. by volum of n-b t ol, n o three hours at 0 i940" nd o ve h urWorkins p is a r ed ou as. de ctihe in xa p e 87 p s 6-0hutyloxy)-'ethane sulfonic acid phenyl ester (67.5% oi the theory) ofthe boiling point 133 to 136 C. at 0.1 to 0.15 mm. Hg is obtained.

Example 4 1.5 parts of sodium metal is dissolved in 500 parts by volumeof tertiary butanol and then 92 parts of; vinylethanesulfonic acidphenyl ester (59% of the theory) of the boiling point 121 to 126 C. at0.1 to 0.2 mm.

H is obtained in addition to 17 parts of residue.

1.5 parts of sodium metal is dissolved in 500 parts by volume ofn-octanol and, while stirring, 92 parts of vinylsulfonio acid phenylester is added. The mixture is kept at to C. for four hours and at C.for another hour. After adding 200 parts by volume of acetone, 14 partsof- B-n-octyloriyethanesulfonic acid sodium salt are filtered oft. Theacetone is evaporated, the residue shaken twice, each time with 200parts by volume of 30% sodium chloride solution and then once with 200parts by volume of sodium bicarbonate solution. The combined Washwatersare extracted with ether and the ethereal solution dried togetherwith the reaction product. Besides 8 parts 1.5 parts of sodium metal isdissolved in 500 parts by volume of butyl diglycol and then 92 parts ofvinylsulfonic acid phenyl ester is added while, stirring constantly. The

Example 11 198 parts of vinylsulfonic acid cresyl ester. is" slowlyadded to 500 parts of allyl alcohol in which 2.5 parts of d y e y powderd c us c so a as en p nded- The mixture is kept at 40 C. for four hoursand then at 50 C. for an hour. The solution is then filtered and thefiltratedistilled. 214 parts of B-(allyloxy)-ethanesultonic acid cresylester (84% of the theory) is obtained with a boiling point of to 142 C.at 0.1 mm. Hg.

Example 12 By proceeding as described in Example 11 but using 500 pa tsof a eio1-L 3 pa s. o sqd um hy roxi powd nd .8 par of vi yl ulfcnic cidcre yl: e er, pa t o l -(4- YQ Q Y J Y1 ISY)' h? lQ Jl 1l c d cre yl e e6% o h eo y). is O a n d th a boilins p int of, 175 to 19.3; C. a to .2mm- H Example 13 4 parts of sodium hydroxide powder is stirred into 500'parts of nonyl alcohol, the whole cooled to 0 C. and 12-2 parts ofvinylsulfonic acid methyl ester allowed to flow in within 30 minuteswhile stirring; The mixture is further stirred for 3 hours at' 0 6.,then for another three hours at room temperature. The precipitate isfiltered off audthe filtrate distilled. 208 parts of B-(nonyl-'oxy)-ethanesulfonic acid methyl 'ester' (78% of the theory) is obtainedwith a boiling point of- 120 to C. at 0.1 to 0.2 mm. Hg. 1

Example 14 By using 500 parts of nonyl alcohol, 198 parts ofvinylsulfonic acid cresyl ester and 0.1 equivalent (equal to 5 parts) ofcalcium methylate and proceeding otherwise as described in Example 5,137 parts of fi-(nonyloxy)- ethanesulfonic acid cresyl ester (40% of thetheory) is obtained with a boiling point of to C. at 0.1 mm. Hg.

7 Example 15 By using 500 parts of Z-ethylhexanol-(l), 198 parts ofvinylsulfonic acid cresyl ester and 0.06 equivalent (equal to 2.4 parts)of finely powdered sodium hydroxide and proceeding as described inExample 11, 275 parts of fi-(2-ethyl-n-hexyl-1-oxy)-ethanesulfonic acidcresyl 8 in 400 parts of isotridecanol is stirred at 10 to 20 C. while212 parts of one of the vinylsulfonic acid xylenol esters set out in thefollowing table is added. The mixture is stirred for another four hoursat room temperature, filtered from solids and the filtrate subjected tofractional distillation. The results are comprised in the "followingester (84% of the theory) is obtained. table:

Ester used fi-alkoxyetbanesultonie acid ester Yield Boiling rangeobtained 2,4-dimethylfl-tridecyloxy-ethanesulfonic 277 parts (67.2% of179196 0.,

phenyl. @A-dlmethylphenyl) ester. the theory). 0.2 mm. Hg

3,5-d1n1ethylfl-trldeeyloxyethanesulfonie 246 parts (59.7% of 175200 Gphenyl. (3 ,5-d1methy1phenyl) ester. the theory). 0.2Emm. Hg

3,4-d1methy1 fi-tridecyloxy-ethanesultonie 356 parts (86.4% of 190-213 Opheuyl. (3,4-d1methylphenyl) ester. the theory). 0.2 mm. Hg.

Example 16 20 Example 21 3 parts of sodium hydroxide powder is stirredinto 460 parts of cyclohexanol and at to 5 C. 198 parts of vinylsulfonicacid cresyl ester is allowed to flow in within 30 minutes, the reactionmixture partly solidifying on the wall of the reaction vessel. Thereaction mixture is allowed to reach room temperature Within two hourswhile stirring and during another three hours the temperature is raisedto 90 C. After cooling to room temperature, the mixture is worked up asdescribed in Example 11. The yield is 249 parts ofB-(cyclohexyloxy)-ethanesulfonic acid cresyl ester (83% of the theory)with a boiling point of 160 to 171 C. at 0.2 mm. Hg.

Example 17 parts of sodium hydroxide powder is stirred into 1000 partsof branched decyl alcohol and at 0 C. 990 parts of vinyl-sulfonic acidcresyl ester is allowed to flow in during 45 minutes. The whole isstirred for another hour at 0 C., heated to room temperature in thecourse of an hour and to 100 C. in the course of another hour and keptfor an hour at this temperature. The mixture is then cooled to roomtemperature and worked up as described in Example 11. p

The yield is 1600 {parts of fl-(branched-decyloxy)- ethanesulfonic acidcresyl ester (90% of the theory) with a boiling point of 170 to 184 C.at 0.02 to 0.05 mm. Hg, 200 .to 214 C. at 5 mm. Hg and 224 to 232 C. at10 mm. Hg.

Example 18 265 parts of C -alcohol from sperm oil is dissolved in 400parts by volume of ether while stirring at about C. Then 2 parts ofsodium hydroxide powder is added and at to C. 122 parts of vinylsulfonicacid methyl ester is added during 30 minutes. The whole is stirred forsix hours at 35 to 40 C., 1 part more of sodium hydroxide powder beingslowly added. The ether is removed in a water pump vacuum. The residueconsists of crude [3-(C -alkoxy-ethanesulfonic acid methyl ester fromwhich by saponification in ethanol with sodium hydroxide 263 parts offi-(C -alkoxy)-ethan-esulfonic acid sodium salt (68% of the theory) isrecovered.

Example 19 0.5 part of sodium hydroxide powder is suspended in parts ofn-octanol, cooled to 0 C. and 66 parts of 1-propene-(1)-sulfonic acidphenyl ester added so that the temperature does not rise above 40 C. Thewhole is then stirred for another eight hours at room tempera ture andworked up as described in 'Example 11.

The yield "is 64 parts of 2-methyl-2-(n-octyloxy)- ethanesulfonic acidphenyl ester (58% of the theory) of the boiling point 162 to 172 C. at0.05 mm. Hg.

Example 20 A suspension of 2.5 parts of sodium hydroxide powder 400parts of isotridecanol and parts of vinylsulfonic acid tert.-butylphenylester are reacted in the presence of 2.5 parts of sodium hydroxidepowder as in Example 20. 105 parts (47.6% of the theory) offi-isotridecyloxyethanesulfonic acid tert.-butylphenyl ester is obtainedwith the boiling point 170 to 207 C. at 0.05 to 0.1 mm. Hg.

Example 22 198 parts of N-methyl-N-B-hydroxyethyl-m-toluidine is mixedat 0 C. with 3 parts of sodium hydroxide powder. 198 parts ofvinylsulfonic acid cresyl ester is stirred into th1s mixture within 15minutes at 0 to +5 C. After half an hour, the whole is heated to roomtemperature and after four hours to about 100 C., kept at thistemperature for 9 hours and then cooled to 0 C. and filtered. Thefiltrate is freed from first runnings (up to 150 C. flask temperature ata pressure of 0.1 mm. Hg). 235 parts of crude adduct is obtained asresidue (about 65% of the theory).

Example 23 To a number of batches, each of 300 parts of allyl alcohol,220 parts of each of the following vinylsulfonic acid esters and 3 to 4parts of sodium hydroxide are added and the whole stirred for threehours at 40 C. Stirring is continued for another 8 hours at roomtemperature, the residue filtered off and the filtrate distilled.

fl-allyloxy-ethanesulfonic acid ester obtained Vinylsulfonie acid esterused B.P. Percent (0.1 mm.), Parts of the C. theory Vinylsulfonieacid-2-chlorophenyl ester- -150 300 79 V nylsulfon c aeid-B-ehlorophenylester. 130-150 250 66 Vmylsulfomc ae1d-4-chlorophenyl ester- 130-150 30079 Example 24 3 parts of sodium hydroxide powder is stirred in smallportions into a mixture of 117 parts of vinylsulfonic acid a-naphthylester and 350 parts of cyclohexanol at 40 to 45 C. during three hours.The whole is allowed to react further for an hour at 80 C, then cooledto room temperature and shaken five times with 200 parts by volume ofwater. The organic layer is dried over sodium sulfate and freed bydistillation from first runnings (up to C. flask temperature at 1 mmHg). The residue is crude ,B-cyclohexyloxyethauesulfonic acid a-naphthylester parts of crude product, yield almost quantitative).

Analysis.-Found: 64.2% C, 6.6% H, 19.2% 0, 9.6%

75 S. Calculated: 66.3% C, 6.1% H, 17.9% 0, 9.5% S.

Example 25 g A mixture of 400 p arts ofn-decanol and 198 parts ofvinylsulfonic acid cresyl ester is stirred at roomtem perature and atotal of 1 parts of eyclohexyltr imethyl ammonium hydroxide is added insmall portions during ten hours. The product is then washed five times,each time with 200 parts by volume of water, the organic layer driedwith sodium sulfate and distilled. 11- par s ("if-W 2v of the theory) ofS-n-decyloxyethanesulfonic acid cresyl ester is obtained with a boilingpoint of 192 to 217 C at 0.3 mm. Hg.

By working in an analogous manner but using phenyltrimethyl ammoniumhydroxide as catalyst, 95 parts (27% of the theory) of ester is obtainedwith the boiling range 183 to 215 C. at 0.2 mm. Hg.

When using isodecanol instead of n-decanol and benzyltrimethyl ammoniumhydroxide as the basic catalyst, 106 parts (equivalent to 30% of thetheory) of fl-isodecyloxyethanesulfonic acid cresyl ester of the boilingrange 165 to 181 C. at 0.1 mm. Hg is obtained under otherwise identicalconditions.

Example 26 214 parts of vinylsulfonic acid guaiacol ester, 500 parts ofn-decanol and 4 parts of sodium hydroxide powder are stirred togetherfor eight hours at 40C. the residue is filtered off by suction and thefiltrate distilled. 244 parts (69% of the theory) offi-n-decyloxyethanesulfonic acid guaiacol ester of the boiling range 180to 220 C. at 0.4 to 0.6 mm. Hg is obtained.

Example 27 198 parts of vinylsulfionic acid, cresyl ester, 600 parts ofN-dimethylethanolamine and 3 parts of sodium hydroxide powder aretreated as described in example 26. After distilling off the firstrunnings up to a flask temperature of 150 C. at a pressure of 3 mm Hg,275 parts of residue remains behind. After washing five times, each timewith 200 parts of water and then drying over sodium sulfate, 190 partsof adduct (crude yield 70%) of the formula:

is obtained.

We claim: 1. A compound of the formula containing at least 9 carbonatoms and in which:

R denotes a member selected from the group consisting of alkyl with 1 to20 carbon atoms, alkenyl with 3 to 20 carbon atoms, cycloalkyl with 5 to12 carbon atoms in the ring, hydroxyalkyl with 2 to 12 carbon atoms,alkoxyalkyl with 3 to 12 carbon atoms, and dialkylaminoalkyl with 4 to23 carbon atoms;

R R and R each denote a member selected from the group consisting ofhydrogen and alkyl with 1 to 3 carbon atoms; and I R denotes a memberselected from the group consisting of phenyl, naphthyl, 5,6,7,8tetrahydronaphthyl, and phenyl and naphthyl substituted by from 1 to 3members selected from the group consisting of alkyl with 1 to 3 carbonatoms, alkoxy with 1 to 3 carbon atoms, halogen and thiocyanate.

. a V 10. 2 A compound of the formula 1 -'CH2QHa7S a'=R5 in which Rdenotes an alkyl group with l to carbon atoms and R d-notes anaryl groupwith 6 to 12: carbon atoms.

3. A compound of the formula V R OCH CH -SO &R

in which R denotes an alkyl group with 1 to 20 carbon atoms and Rdenotes an alkoxy-aryl group with 7 to 13 carbon atoms.

' 4. A compound of the formula in which R denotes a member selected fromthe group consisting of alkyl with 1 to 20 carbon atoms, alkenyl with 3to 20 carbon atoms, cycloalkyl with 5 to 12 carbon atoms in the ring,hydroxyalkyl with 2 to 12 carbon atoms, alkoxyalkyl with 3 to 12 carbonatoms, and dialkylaminoalkyl with 4 to 23 carbon atoms; R R and R eachdenote a member selected from the group consisting of hydrogen and alkylwith 1 to 3 carbon atoms; and R denotes a member selected from the groupconsisting of alkyl with 1 to 6 carbon atoms, phenyl, naphthyl,5,6,7,S-tetrahydronaphthyl, and phenyl and naphthyl substituted by from1 to 3 members selected from the group consisting of alkyl with 1 to 3carbon atoms, alkoxy with 1 to 3 carbon atoms, halogen and thiocyanate,which process comprises: a

mixing a vinylsulfonic acid ester of the formula CR2R3=CR4SO20-R5, inR2, R3, R4 and R are as previously defined, with a stoichiometric excessof an alcohol of the formula R OH, in which R is as previously defined,in the presence of 0.02 to 0.1 equivalent of a compound selected fromthe group consisting of alkali and alkaline earth metal alcoholates ofthe alcohol reactant R OH, alkali and alkaline earth metal alcoholatesof alkanols with 1 to 4 carbon atoms, alkali metal hydroxides andquaternary ammonium bases of the formula R!!! {l /N :lon

RI! \RIIII in which R, R" and R'" each denote alkyl with 1 to 3 carbonatoms and R"" denotes a hydrocarbon radical selected from the groupconsisting of aryl of 6 to 10 carbon atoms, aralkyl with 7 to'8 carbonatoms and cycloalkyl with 5 to 12 carbon atoms in the ring, at atemperature between 10 C. and 0., and separating said alkanesulfonicacid ester formed thereby.

9. A process as claimed in claim 8 wherein said reaction is carried outin an inert organic solvent.

(References on following page) 1 1 1 2 References Cited by the ExaminerJohary et a1.: J. Chem. Soc. (London), vol. of 1955,

UNITED STATES PATENTS 1307-1311- 1985 747 12/34 Steindorfi et al 260 512K9oh)ler et a1.: Am. Iour. Chem, v01. 20, page 690 18 8 2 094 489 9/37Hueter et a1 260-513 o Wagner et a1.. Synthetxc Orgamc Chemlstry, page232 2,474,350 6/49 Ellerman 260-456 (1953)- OTHER REFERENCES Chapman etal.: J. Chem. Soc. (London), vol. of CHARLES PARKER P "mary Examiner1950, pp. 579-585. JOSEPH P, BRUST, Examiner.

1. A COMPOUND OF THE FORMULA